JP2504273B2 - Microwave / millimeter wave magnetic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a magnetic material composition used in a high frequency region such as a microwave and a millimeter wave.

<Prior Art> Conventionally, Mn-Mg ferrite, Ni-Zn ferrite, lithium ferrite, YIG ferrite, etc. have been used as high frequency magnetic material.

These are excellent materials with saturation magnetization (4πMs) values of 500-4000 Gauss.

Among these, MIG ferrite is a product of U.S. Pat.
As shown in No. 05, the composition consisting of Y ₃ Fe ₅ O ₁₂
By substituting Al for Gd and Al, the temperature coefficient (α) of 4πMs and 4πMs can be changed, so that the material having the most suitable value of 4πMs for the frequency to be used can be selected and used in combination with the permanent magnet. In this case, it is an excellent material that can compensate the temperature characteristics of the magnet, and is a material that can be applied to circuit elements such as highly stable isolators and circulators.

According to U.S. Pat.No. 3,419,496, this material has a low volume resistivity ρ of 7.0 × 10 ⁸ Ωcm, but it can be increased to 4.9 × 10 ¹² Ωcm by adding MnO _2. Has been done. Further, according to Japanese Patent Publication No. 60-55970,
When the mixing ratios of the raw materials Y ₂ O ₃ and Fe ₂ O ₃ are set to 38.63 to 39.45 mol% and 61.37 to 60.55 mol%, respectively, the ferromagnetic resonance absorption half width (ΔH) can be reduced to 16 oersteds. There is.

<Problems to be Solved by the Invention> However, YIG ferrite has a problem of ΔH and dielectric loss (T
It has a drawback that the value of loss such as an δ) becomes so large that it practically hinders due to subtle compositional variations.
Further, when using this material for the phase conversion element, a high residual magnetic flux density (Br) is required, but there is a problem that tan δ also increases when Br is increased.

The present invention in consideration of the above problems, has been made for improving the drawbacks of the conventional YIG ferrite, Y _w Fe _8-w O
₁₂ of the YIG ferrite represented by the general formula
And at the same time cobalt oxide and zirconium oxide are added to achieve a very small ΔH value.
An object of the present invention is to provide a microwave / millimeter wave magnetic material in which a large Br value and a small tan δ value are realized at the same time by fixing the ratio of sites to Fe sites within a very limited and narrow range.

Further, it is intended to replace a part of Y with Gd so that α can be set to an arbitrary value, or to replace a part of Fe with Al so that 4πMs can be set to an arbitrary value. .

<Means for Solving the Problems> As a result of intensive research for solving the above problems, the present inventors have found that a part of Fe sites in YIG ferrite represented by the general formula of Y _w Fe _8-w O _12. It was found that an extremely small ΔH can be obtained by substituting cobalt oxide and zirconium oxide at the same time as substituting Mn for Mn, and further, in a very narrow region where the ratio w of Y site and Fe site is between 3.02 and 3.06, a large Br is obtained. We have found that a small tan δ can be realized at the same time.

That is, in order to solve the above-mentioned problems, the magnetic substance composition for microwaves / millimeter waves of the present invention has Y _w (Fe _1-z Mn _z )
_{In the} composition represented by _8-w O ₁₂ , z and w are 0.
Cobalt oxide and Z expressed in the form of CoO, with a composition of 01 ≦ z ≦ 0.04, 3.02 ≦ w ≦ 3.06 as the main component
It is characterized in that zirconium oxide expressed in the form of rO ₂ is added in an amount of 0.05 mol% or more and 0.2 mol% or less, respectively.

Further, in the present invention, it was found that a part of Y can be replaced with Gd to set α to an arbitrary value, and / or a part of Fe can be replaced with Al to set 4πMs to an arbitrary value. in _{(Y 1-x Gd x)} w (Fe 1-yz Al y Mn z) composition expressed in _{8-w O 12, x,} y, z, and w are each 0 ≦
x ≦ 0.35, 0 ≦ y ≦ 0.16 (however, when one of x and y is 0, the other does not include 0), 0.01 ≦ z ≦ 0.0
4, with a composition in the range of 3.02 ≦ w ≦ 3.06 as the main component, cobalt oxide expressed in the form of CoO and zirconium oxide expressed in the form of ZrO ₂ of 0.5 mol% or more,
0.2 mol% or less can be added and contained.

<Operation> According to the present invention, 4πMs can be arbitrarily set in the range of 320 to 1750 gauss, and therefore, a material having a value of 4πMs most suitable for the frequency used can be selected.

Further, since α can be arbitrarily set within the range of −820 to −2550 ppm / ° C., the temperature characteristic of the magnet can be compensated when used in combination with a permanent magnet or the like.

Furthermore, since Br is high and the value of loss such as ΔH and tanδ is extremely small, it is possible to obtain a magnetic material for micro-millimeter wave suitable for application to a latching phase converter, a high-precision isolator and a circulator. .

Regarding the above-mentioned objects, features and advantages of the present invention,
Examples will be described below with reference to the drawings.

<Example> First, as a raw material, high purity _{Y 2 O 3, Fe 2 O} 3, Gd 2 O 3, Al
₂ O ₃ , MnO ₂ , Co ₃ O ₄ and ZrO ₂ were prepared. These raw materials were weighed so that the compositions shown in Table 1, Table 2 and Table 3 were obtained, and wet-mixed for 16 hours in a ball mill. After this mixture was dried, it was calcined at 1050 ° C. for 2 hours to obtain a calcined product. This calcined product was put into a ball mill together with an organic binder and wet-milled for 16 hours. After drying this crushed product,
2000 kg of powder obtained by granulating through a 50 mesh net
It was molded into a prism of 3 mm × 3 mm × 20 mm and a ring having an outer diameter of 36 mm, an inner diameter of 24 mm, and a thickness of 6 mm at a pressure of / cm ² . These molded products were fired at 1460 to 1490 ° C. for 8 hours. Of these, the prismatic sintered body was machined to obtain a sphere with a diameter of 1.3 mm and a diameter of 1.3 mm.
A cylindrical sample having a length of 1.3 mm and a length of 16 mm was obtained.

Of the obtained samples, the temperature coefficient (α) and Curie temperature (Tc) of 4πMs and 4πMs of the spherical sample were measured using a vibrating magnetometer and measured in a TE106 cavity resonator.
ΔH at 0 GHz was measured.

Also, tan δ at 10 GHz was measured for the cylindrical sample in the TM101 cavity resonator by using the displacement method.

Further, with respect to the ring-shaped sample, the toroidal coil was formed by winding the conductor wire into a bifilar winding, and the residual magnetic flux density (Br) and the coercive force (Hc) at 100 Hz were measured.

Table _{1, (Y 1-x Gd x} ) w of _{(Fe 1-yz Al y Mn} z) 8-w O 12 with a composition represented by changing the x and y, and expressed in the form of CoO the measurement results obtained by changing the amount of zirconium oxide expressed in the form of cobalt oxide and ZrO _2. The * mark in Table 1 is outside the scope of the present invention, and everything else is within the scope of the present invention. Furthermore, the first
The composition ranges of the experimental examples shown in the table are shown in the composition diagram of FIG. The numbers in this figure represent the sample numbers. In FIG. 1, a region showing a composition ratio within the scope of the present invention is shown by a quadrangle having vertices A, B, C and D.

_{Here, (Y 1-x Gd x} ) w (Fe 1-yz Al y Mn z) 8-w represented by the composition by O _12, x and y respectively 0 ≦ x ≦ 0.35,0
The reason for limiting the range to ≦ y ≦ 0.16 will be described.

When y exceeds 0.16 as in Sample Nos. 7, 14, 21 and 25, Br decreases and Tc decreases, which is not preferable.

Also, x is 0.35 as in sample numbers 22, 23, 24 and 25.
If it exceeds, ΔH becomes large, which is not preferable.

Next, the addition amount of cobalt oxide expressed in the form of CoO and zirconium oxide expressed in the form of ZrO ₂ was adjusted to 0.05% respectively.
The reason for limiting the content to not less than mol% and not more than 0.2 mol% will be described.

First, sample numbers 2, 9 and 16 are examples in which the amounts of CoO and ZrO ₂ added are each 0 mol%, and are excluded from the scope of the present invention.

Samples Nos. 3, 10 and 17, in which the amounts of CoO and ZrO ₂ added are each less than 0.05 mol%, are not significantly improved in ΔH and are excluded from the scope of the present invention.

Samples Nos. 5, 12 and 19 in which the amounts of CoO and ZrO ₂ added each exceeded 0.2 mol% were not preferable because ΔH increased and Br decreased.

Here, the action of ZrO ₂ is to make the total valence of (Y _1-x Gd _x ) _w ( Fe _1-yz Al
_y Mn _z ) _8-w O ₁₂ of the composition is to charge each ion into the (Fe _1-yz Al _y Mn _z ) site without charge. Therefore, instead of ZrO ₂ , SiO ₂ , TiO ₂ , GeO ₂ , Sn
The same effect can be obtained by using a tetravalent ion oxide such as O ₂ or HfO ₂ .

Next, Table 2 shows (Y _1-x Gd _x ) _w (Fe _1-yz Al _y Mn _z ).
It is a measurement result when changing z of the composition represented by _8-w O ₁₂ .

Sample Nos. 26 to 30 in Table 2 are sample No. 4 in Table 1.
No. 31 to 35 in Table 2 are obtained by changing z with respect to the composition of Sample No. 11 in Table 1. Sample Nos. 31 to 35 in Table 2 are obtained by changing z with respect to the composition of Sample No. 11 in Table 1. Number 36-
No. 40 changes z about the composition of sample No. 18 in Table 1.

The asterisk * in Table 2 is outside the scope of the invention, and everything else is within the scope of the invention. The composition ranges of the experimental examples shown in Table 2 are shown in the composition diagram of FIG. 1 as in Table 1. The numbers in this figure represent the sample numbers.

Here it will be described the reason for limiting the _{(Y 1-x Gd x)} w (Fe 1-yz Al y Mn z) 8-w O represented in the composition by at _12, z and 0.01 ≦ z ≦ 0.04.

When z is less than 0.01 as in sample numbers 26, 31 and 36, ΔH becomes large, which is not preferable.

Further, when z exceeds 0.04 as in sample numbers 30, 35 and 40, ΔH becomes large, which is not preferable.

Finally, Table 3 shows (Y _1-x Gd _x ) _w (Fe _1-yz Al _y Mn _z ).
It is a measurement result when w of the composition represented by _8-w O ₁₂ is changed.

Sample Nos. 41 to 45 in Table 3 are sample No. 4 in Table 1.
No. 46 to 50 in Table 3 are those in which w is changed, and w in the composition of Sample No. 11 in Table 1 is changed. Number 51-
55 is the composition of sample No. 18 in Table 1 with w changed.

* In Table 3 is outside the scope of the present invention, and everything else is within the scope of the present invention. The composition ranges of the experimental examples shown in Table 3 are shown in the composition diagram of FIG. 1 as in Tables 1 and 2. The numbers in this figure represent the sample numbers.

_{Here, (Y 1-x Gd x} ) w (Fe 1-yz Al y Mn z) 8-w O ₁₂ represented by the composition, the reasons for limiting the w in the range of 3.02 ≦ w ≦ 3.06 3 This will be described with reference to the table and FIG.

When w is less than 3.02 as in sample numbers 41, 46 and 51, tan δ becomes large, which is not preferable.

When w exceeds 3.06 as in sample numbers 45, 50 and 55, ΔH increases and Br decreases, which is not preferable.

FIG. 2 shows (Y _1-x Gd _x ) _w for sample numbers 46 to 50
(Fe _1-yz Al _y Mn _z ) _8-w O ₁₂ Common logarithm of w and tan δ (lo
It shows the relationship between g tan δ) and Br. Second
As is clear from the figure, a large Br and a small tan δ can be simultaneously realized only in the range of w of 3.02 ≦ w ≦ 3.06. The numbers in FIG. 2 represent the sample numbers.

<Effects of the Invention> As described above in detail, the microwave / millimeter wave magnetic material composition according to the present invention has sufficiently small ΔH and sufficiently small tan δ, and also has high Tc and large Br. Therefore, it is a very useful material for application to circuit elements such as latching type phase converters, highly stable isolators and circulators. Furthermore, (Y _1-x Gd _x ) _w (Fe _1-yz
By appropriately changing x and y represented by the chemical formula of Al _y Mn _z ) _8-w O ₁₂ within the scope of the present invention, 4πMs
It can be arbitrarily set in the range of 320 to 1750 gauss, and / or α can be arbitrarily set in the range of -820 to -2550 ppm / ° C. Therefore, it is possible to select a material having a value of 4πMs most suitable for the frequency to be used, and it is possible to compensate the temperature characteristic of the magnet when used in combination with a permanent magnet or the like.

[Brief description of drawings]

In Figure 1 the microwave and millimeter wave for magnetic composition according to the present _{invention, (Y 1-x Gd x} ) w (Fe 1-yz Al y Mn z) 8-w O 12 of x
FIG. 2 is a composition diagram showing the composition range of y and y. FIG. 2 shows (Y _1-x Gd _x ) _w (Fe _1-yz Al _y M for sample numbers 46 to 50 in Table 3).
2 is a graph showing a relationship between _{w of} n _z ) _8-w O ₁₂ and a common logarithmic value (log tan δ) of tan δ, and Br.

Claims (2)

(57) [Claims] 1. In the composition represented by Y _w (Fe _1-z Mn _z ) _8-w O ₁₂ , z and w are 0.01 ≦ z ≦ 0.04 and 3.02 ≦ w ≦, respectively.
A microwave containing as a main component a composition in the range of 3.06, containing 0.05 mol% or more and 0.2 mol% or less of cobalt oxide expressed in the form of CoO and zirconium oxide expressed in the form of ZrO ₂ , respectively. Magnetic substance composition for millimeter waves. 2. A _{(Y 1-x Gd x)} w (Fe 1-yz Al y Mn z) composition expressed in _{8-w O 12, x,} y, z, and w are each 0 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.16 (however, when one of x and y is 0, the other does not include 0), 0.01 ≦ z
Cobalt oxide and ZrO ₂ expressed in the form of CoO, whose main component is a composition in the range of ≦ 0.04, 3.02 ≦ w ≦ 3.06
0.5 mol% of zirconium oxide in the form of
As described above, a magnetic material composition for microwaves / millimeter waves, containing 0.2 mol% or less.